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第 36 卷第 7 期 精 细 化 工 Vol.36, No.7
201 9 年 7 月 FINE CHEMICALS J u l y 2019

催化与分离提纯技术
Brønsted 酸性离子液体催化双酚芴的合成

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闫 磊 ，于丽梅 1,2* ，申茂昌 ，高占先 1,2
（1. 大连理工大学 化学学院，辽宁 大连 116024；2. 大连理工大学 精细化工国家重点实验室，辽宁
大连 116024）

摘要：以 1-甲基咪唑、1,3-丙磺酸内酯、硫酸、磷酸、四氟硼酸、对甲苯磺酸为原料，合成 4 种 Brønsted 酸性
离子液体（ILs），通过 FTIR、NMR 和 TG 对其结构进行了表征，同时采用 UV-vis 测定了离子液体的酸度 H 0 。
将离子液体应用于双酚芴（BHPF）的合成反应中，离子液体的酸度 H 0 ≤1.94 时有催化作用，H 0 ≤1.69 的 ILs
催化剂有应用价值。采用单变量优化法考察了反应参数对 9-芴酮和苯酚缩合反应的影响，确定较优反应条件为：
苯酚、9-芴酮和 IL1 的物质的量比为 6∶1∶0.125，IL1 和助催化剂巯基乙酸的物质的量比为 5∶2，反应温度 110
℃，反应时间 6 h。在上述条件下，考察了 4 种离子液体催化剂对双酚芴合成反应的催化效果，使用 IL1、IL2、
IL4 催化反应时，9-芴酮转化率均为 100%，双酚芴的选择性约为 87%。此外，离子液体 IL1 连续使用 5 次催化
效果无明显降低。
关键词：离子液体；9-芴酮；双酚芴；缩合反应；助催化剂；催化技术
中图分类号：O625.3 文献标识码：A 文章编号：1003-5214 (2019) 07-1357-07

Brønsted Acidic Ionic Liquid Catalyzed Synthesis of Bisphenolfluorene

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YAN Lei , YU Li-mei 1,2* , SHEN Mao-chang , GAO Zhan-xian
（1. School of Chemistry, Dalian University of Technology, Dalian 116024, Liaoning, China; 2. State Key Lab of Fine
Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China）
Abstract: Four Brønsted acidic ionic liquids (ILs) were synthesized using 1-methylimidazole, 1,3-propane
sultone, sulfuric acid, phosphoric acid, tetrafluoroboric acid and p-toluene sulfonic acid as raw materials.
Their structures were characterized by FTIR, NMR and TG and the acidity H 0 was measured by UV-vis.
These ionic liquids were applied to the synthesis of bisphenolfluorene. When the H 0 was less than or equal
to 1.94, the ionic liquid had catalytic effect, when that was less than or equal to 1.69, the ionic liquid had
applicable value. A method for the determination of bisphenolfluorene by liquid chromatography was
developed. The reaction products were separated and the structures of the three products were determined
by NMR. The effect of reaction parameters on the condensation reaction of 9-fluorenone and phenol was
investigated by univariate optimization. The optimal reaction conditions were obtained as follows∶
n(phenol) ∶ n(9-fluorenone) ∶ n(IL1)=6 ∶ 1 ∶ 0.125, n(IL1) ∶ n(thioglycolic acid)=5 ∶ 2, reaction
temperature 110 ℃ and reaction time 6 h. The catalytic effects of the four catalysts in the synthesis of
bisphenolfluorene were investigated under the above conditions. For IL1, IL2 and IL4 catalysts, the
conversion of 9-fluorenone was 100%, and the selectivity of bisphenolfluorene was nearly 87%. In addition,
the catalytic effect of ionic liquid IL1 was not significantly reduced after 5 consecutive uses.
Key words: ionic liquids; 9-fluorenone; bisphenolfluorene; condensation reaction; co-catalyst; catalysis
technology

9,9-双（4-羟基苯基）芴（简称双酚芴，BHPF） 中。含双酚芴结构的聚合物材料具有良好的刚性、
是一种重要的精细化工原料，广泛应用于环氧树 耐热性、光学性能及成型性等，在军事、航空航
脂、聚氨酯、聚碳酸酯和聚醚砜等聚合物的生产 天、燃料电池、电光材料和汽车工业中具有广阔的

收稿日期：2019-01-15; 定用日期：2019-03-07; DOI: 10.13550/j.jxhg.20190052
作者简介：闫 磊（1992—），男，硕士生。联系人：于丽梅（1971—），女，副教授，E-mail：ochem@dlut.edu.cn。